CN104874365A - Carboxymethyl cellulose ion intercalated hydrotalcite-like composite material, and preparation method and application thereof - Google Patents
Carboxymethyl cellulose ion intercalated hydrotalcite-like composite material, and preparation method and application thereof Download PDFInfo
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- CN104874365A CN104874365A CN201510275874.2A CN201510275874A CN104874365A CN 104874365 A CN104874365 A CN 104874365A CN 201510275874 A CN201510275874 A CN 201510275874A CN 104874365 A CN104874365 A CN 104874365A
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- hydrotalcite
- composite material
- carboxymethyl cellulose
- ldo
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 60
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 34
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 46
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011229 interlayer Substances 0.000 claims abstract description 14
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000009830 intercalation Methods 0.000 claims abstract description 7
- 230000002687 intercalation Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 5
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 17
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000003780 insertion Methods 0.000 claims description 9
- 230000037431 insertion Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims description 8
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002905 metal composite material Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 26
- 239000003463 adsorbent Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 abstract description 5
- 239000013535 sea water Substances 0.000 abstract description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010612 desalination reaction Methods 0.000 abstract 1
- 239000005447 environmental material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910003023 Mg-Al Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- FYSNRPHRLRVCSW-UHFFFAOYSA-N dodecasodium;tetraborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] FYSNRPHRLRVCSW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical group 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a carboxymethyl cellulose ion intercalated hydrotalcite-like composite material, and a preparation method and application thereof. The chemical formula of the composite material is [M<2+>1-x M<3+>x (OH)2]<x+> (A<->)x.mH2O, wherein M<2+> is Zn<2+>, Ca<2+> or Mg<2+>, M<3+> is Fe<3+> or Al<3+>, M<2+> and M<3+> are located on a hydrotalcite main body laminate; A<2-> represents an interlayer carboxymethylcellulose anion; x is the molar ratio of M<3+> to (M<2+> + M<3+>), wherein x is greater than or equal to 0.1 and less than or equal to 0.33; m represents the number of interlayer water molecules, and can be 3, 4, 5 or 6. The hydrotalcite-like composite material adopts a calcining intercalation method, o-hydroxy-rich carboxymethyl cellulose anions are assembled between hydrotalcite-like layers in an intercalated manner to prepare the hydrotalcite-like composite material with a typical lamellar structure as an adsorbent applied to selective adsorption removal of borate root anions in water; the composite material can be used as a novel environmental material for boron separation and adsorption in wastewater and seawater desalination, is high in thermal stability and mechanical stability, environmentally-friendly, and simple in preparation process, and can realize industrialization easily.
Description
Technical field
The invention belongs to technical field of inorganic-organic composite function material preparation, be specifically related to one
carboxymethyl cellulose ion insertion hydrotalcite-like composite material and preparation method thereof and application.
Background technology
Along with the development of economic society, current environment pollutes the significant challenge becoming facing mankind, and various water pollution constantly aggravates, and causes the continuous deterioration of ecological environment, drastically influence the Health and Living quality of people.Wherein, boron is as a kind of important industrial chemicals, and practical application is extensive, but the boron pollution that waste water containing boron discharge produces is urgently to be resolved hurrily.At present, can be used for being separated the adsorbent removing boron in solution and mainly can be divided into inorganic adsorbent, organic polymer adsorbent and hybrid boron adsorbent three kinds.Inorganic Boron adsorbent has firmly structure, good heat endurance and lower preparation cost, but lower and not have special efficacy selective to the adsorption capacity of boron, is subject to the impact of coexisting ion.Organic adsorbent with N-methyl glucose osamine for adsorption functional group has special efficacy selectivity and higher adsorption capacity to boron, but due to its structural particularity and water-insoluble, make it show the defect such as mechanical performance and hydrophily difference in actual applications, have a strong impact on the performance of its performance.Now in the urgent need to finding an a kind of or class to have high stability, selective height, adsorbent fast with low cost and efficient to the focus that to realize the efficient removal of boron be current absorption method studies except boron and difficult point.Composite is the trend of modern material development, and realize performance complement and optimization by the compound of multiple material function, wherein organic/inorganic hybridization material is nova the most dazzling in compositional material families.Chinese scholars is attempted by by adjacent hydroxy compounds load or graft on mesoporous material or silica gel and prepare hybrid boron adsorbent.
Cellulose is the abundantest the most ancient natural polymer on the earth, is the most valuable natural reproducible resources of the inexhaustible mankind.Carboxymethyl cellulose (CMC) is base stock with native cellulose, is the cellulose kind that in the world today, the scope of application is the widest, consumption is maximum.It is with low cost, through alkalization, etherification reaction and a kind of electrolytic polymer of generating.Owing to containing many hydrophilic hydroxyls and carbonyl in carboxymethyl cellulose molecule, therefore to metal ion and dyestuff, there is certain adsorptivity.But the ability of its adion is not strong, must make it have more or stronger hydrophilic radical by chemical modification, to reducing costs, improving SNR, become sorbing material of good performance.
Houghite (LDHs), has the double-metal hydroxide of layer structure as a class, the advantage such as heat endurance of the composition of modulation, high surface adsorption property and uniqueness can cause the extensive concern of researcher because it has.When LDHs interlayer ion is CO
3 2-, NO
3 -and Cl
-during Deng inorganic ions, hydrotalcite can be used for the boron in adsorbent solution, but adsorption capacity is not high.At houghite interlayer, the organic acids such as insertion tartaric acid, citric acid and malic acid can be used for the metal ion in adsorbed water.Have been reported organic matter introduced houghite interlayer can prepare many with precursor phase than the functional material with property.
The novel hybrid boron adsorbent that the carboxymethyl cellulose ion insertion being rich in adjacent hydroxyl is prepared to houghite interlayer will be obtained significantly result.Houghite interlayer is due to the introducing of carboxymethyl cellulose on the one hand, not only can produce selective absorption as adsorption activity center to boron, and interface polarity and the chemical micro-environment of material can be improved, interlamellar spacing is increased, reduce surface energy, adsorption capacity can significantly strengthen; On the other hand due to the introducing of houghite inorganic material matrix, this sorbing material can be made to have higher mechanical stability and heat endurance, and be conducive to regeneration and recycle.Add houghite and these two kinds of raw material sources of carboxymethyl cellulose extensive, cost is low, and Environmental compatibility is good, and such adsorbent will be had broad application prospects.But, yet there are no the report of preparation about the anion intercalated houghite of carboxymethyl cellulose and attracts boron thereof.
Summary of the invention
The object of the present invention is to provide a kind of carboxymethyl cellulose intercalation hydrotalcite-like composite material with low cost, easy to make, this material environment is friendly, heat endurance and mechanical stability high, high to the adsorption capacity of boron at normal temperatures, can be used for boron in water body separation remove.
For achieving the above object, the technical solution adopted in the present invention is:
Hydrotalcite-like composite material of the present invention adopts calcining graft process, be assembled into houghite interlayer by anion intercalated for the carboxymethyl cellulose being rich in adjacent hydroxyl and prepare the hydrotalcite-like composite material with typical layers laminated structure, the features such as this product has heat endurance and mechanical stability is high, environmental friendliness, and preparation technology is simple, easily realizes industrialization.A large amount of adjacent oh group in this kind of composite organic-inorganic material can play chelating suction-operated to boron, and what can be used for waste water and boron in desalinization is separated absorption.This kind of anion intercalated hydrotalcite-like materials of carboxymethyl cellulose and existing boron adsorbent are as compared with except boron resin etc., not only mechanical strength is large, preparation cost is low, boron adsorption capacity is high, and have significant special efficacy suction-operated to the boron in solution, be expected to industrially be applied as a kind of novel boron special efficacy sorbing material.
The chemical general formula of a kind of carboxymethyl cellulose ion insertion hydrotalcite-like composite material of the present invention is
[M
2+ 1-xm
3+ x(OH)
2]
x+(A
-)
xmH
2o, wherein M
2+for Zn
2+, Ca
2+or Mg
2+, M
3+for Fe
3+or Al
3+, M
2+and M
3+be positioned on hydrotalcite main body laminate; A
2-for interlayer carboxymethyl cellulose anion; X is M
3+/ (M
2++ M
3+) molar ratio, 0.1≤x≤0.33; M is the number of intermediary water molecule, m=3-6; The crystal structure of this kind of material is the crystal structure of hydrotalcite-like materials;
The preparation method of a kind of carboxymethyl cellulose ion insertion hydrotalcite-like composite material of the present invention, comprises the following steps:
1) be dissolved in deionized water by soluble divalent metal salt and trivalent metal salt by certain mol proportion, stir to obtain solution A, wherein divalence and trivalent metal metal ion mol ratio are (1 ~ 4): 1, and bivalent metal ion concentration is 0.05 ~ 0.10 molL
-1;
2) under strong stirring, sodium hydroxide solution is dropwise added drop-wise in solution A, pH to 9 ~ 10 are regulated with sodium hydroxide solution, at room temperature Keep agitation 1 ~ 3h, by gained mixture filtering and washing for several times to neutral, thermostatic drying chamber 80 ~ 120 DEG C of drying 4 ~ 6h put into by gained filter cake, obtain white solid B, i.e. layered double hydroxide material LDH;
3), after calcining 3 ~ 5h at above-mentioned gained solid B being placed in Muffle furnace 300 ~ 600 DEG C, white solid powder C is obtained, i.e. layered bi-metal composite oxides LDO;
4) by above-mentioned obtained layered bi-metal composite oxides LDO, be scattered in by a certain percentage in deionized water, obtain suspension D;
5) sodium carboxymethylcellulose solid is dissolved in distilled water, obtains carboxymethylcellulose sodium solution E;
6) by above-mentioned steps 4) in the LDO suspension D of gained, mix with a certain proportion of carboxymethylcellulose sodium solution E, mechanical agitation 6 ~ 10h, solution alkaline pH8 ~ 10 in maintenance flask; Crystallization 12 ~ 20h in 80 ~ 150 DEG C of baking ovens in hydrothermal crystallizing still said mixture being transferred to polytetrafluoroethylene (PTFE), be cooled to room temperature, products obtained therefrom Separation of Solid and Liquid, washing is to neutral rear 60 ~ 85 DEG C of vacuum drying 2 ~ 10h, obtain the hydrotalcite-like composite material that carboxymethyl cellulose is anion intercalated, be designated as LDH-CMC.
Described divalent metal divalent metal salt is Zn
2+, Ca
2+or Mg
2+nitrate, trivalent metal salt is Fe
3+or Al
3+nitrate.
Described naoh concentration is 0.50 ~ 4.0 molL
-1, the mixing speed of described strong stirring is 300 ~ 450rpm.
The mol ratio of described sodium carboxymethylcellulose and trivalent salt is 1:1 ~ 3:1.
Described layered bi-metal composite oxides LDO and the mass ratio of deionized water are 1% ~ 3%, and the concentration of described carboxymethylcellulose sodium solution E is 1% ~ 3%, and described LDO suspension D and the volume ratio of carboxymethylcellulose sodium solution E are 1:1 ~ 1:3.
Utilize adjacent oh group to the chelating principle of boron, using hydrotalcite-like composite material anion intercalated for the carboxymethyl cellulose being rich in adjacent oh group of above-mentioned preparation as adsorbent, the selective absorption being applied to water body mesoboric acid root anion is removed.
The present invention compared with prior art has the following advantages:
1) this technology adopts calcining graft process can synthesize the LDH-CMC boron in solution to special efficacy adsorption selection ability of particle diameter and morphology controllable, thus has expanded the type of boron adsorbent; In addition, this method resulting materials entirety is homogeneous, chemical composition and structure is adjustable on microcosmic;
2) by the anion intercalated LDH-CMC obtained of carboxymethyl cellulose compared with common LDH, there is more adjacent oh group, the selective of product boron and adsorption capacity can be improved further, can efficient adsorption boron at short notice; The advantages such as it is high that LDH-CMC has mechanical strength compared with common CMC, easy recovery;
3) this technology gained organic/inorganic composite material is adopted to have feature that is inorganic, organic adsorbent concurrently, with traditional boron adsorbent as compared with except the inorganic adsorbent such as organic adsorbent or hydrous oxide such as boron resin, there is the advantages such as mechanical strength is large, adsorption capacity is high, special efficacy is selective, low price;
4) this technology is simple and easy to do, pollution-free, practical, products obtained therefrom applied range.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1.
Fig. 2 is Fourier transform infrared (FTIR) figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1.
Fig. 3 is thermogravimetric weightlessness (TG-DSC) figure of Mg-Al-LDH and Mg-Al-CMC in embodiment 1.
Fig. 4 is high-resolution field emission scanning electron microscope (HRSEM) figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1.
Fig. 5 be in embodiment 1 Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC to the adsorption effect figure of boron.
Fig. 6 be in embodiment 1 in Mg-Al-CMC and embodiment 2 Mg-Al-CMC2 to the adsorption effect comparison diagram of boron.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is described further, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1
(1) mol ratio is the synthesis of the Mg-Al houghite of 2: by 5.12g magnesium nitrate and 3.75g aluminum nitrate, be dissolved in 100mL
Mixed solution is made in distilled water; Then 4g NaOH is dissolved in 100mL distilled water and is made into mixed ammonium/alkali solutions.Two solution are instilled in the three-neck flask having filled 100mL distilled water under room temperature constantly stirs.After dropwising, use 1molL
-1naOH regulates pH to 9-10, at room temperature Keep agitation 2h.By gained mixture filtering and washing for several times to neutral, thermostatic drying chamber 80 DEG C of dry 4h put into by gained solid, obtain Mg-Al double-metal hydroxide Mg-Al-LDH.
(2) Mg-Al-LDH solid is positioned in Muffle furnace and calcines after 4 hours at 450 DEG C, obtain white solid Mg-Al
Bimetallic oxide Mg-Al-LDO.
(3) this Mg-Al-LDO ultrasonic cleaner is scattered in 100mL distilled water obtains Mg-Al-LDO suspension.
(4) take 4.5g sodium carboxymethylcellulose (being called for short CMC) after dissolving, to be added drop-wise in 100mL distilled water
In Mg-Al-LDO suspension, mechanical agitation 4 hours, keeps solution alkaline pH 9-10 in flask; Crystallization 12 hours in 80 DEG C of baking ovens in the hydrothermal reaction kettle its mixture being transferred to polytetrafluoroethylene (PTFE), filter, washing to neutral, dry at 80 DEG C, grinding, obtains Mg-Al-CMC sample.
Fig. 1 is X-ray diffraction (XRD) figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1.As can be seen from the figure, in 2 θ=11.26 °, 22.8 °, 34.34 °, 60.50 °, 61.64 ° places, products obtained therefrom Mg-Al-LDH all shows the characteristic diffraction peak (003) of houghite, (006), (009), (110), and prepared sample diffraction peak height and narrow, assorted peak is little, and the houghite prepared by explanation is the high single crystalline phase of degree of crystallinity.By the Mg-Al-LDO obtained after the 400 DEG C of roastings of Mg-Al-LDH solid, Mg-Al-LDH crystal characteristic diffraction maximum disappears completely, has occurred the characteristic diffraction peak of bimetal composite oxide (LDO) simultaneously.By the Mg-Al-CMC that CMC intercalation Mg-Al-LDO obtains, Mg-Al-LDH crystal characteristic peak occurs again, and obviously to low-angle skew, illustrate that the layer structure of houghite is restored, gained composite has the crystal structure identical with houghite.
Fig. 2 is Fourier transform infrared spectroscopy (FTIR) figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1.At 3400cm in figure
-1locate the stretching band that wider bands of a spectrum are physical absorption water or the crystallization water-OH vibrational band and M-OH, in addition at 1630cm
-1also there are the weak flexural vibrations bands of a spectrum of water at place.At 780 ~ 890cm
-1place is M-O vibrational band.After CMC is intercalation into Mg-Al-LDH, 1630 cm
-1near the vibration peak of the crystallization water substantially return to level before roasting, at 1380cm
-1there are the symmetrical stretching vibration bands of a spectrum of carboxylate radical-COO-, and at 1040cm
-1there is C-O stretching vibration peak.FT-IR spectrogram illustrates that CMC has entered the inter-layer position of Mg-Al-LDO, achieves the intercalation assembling of carboxymethyl cellulose pillared hydrotalcite supramolecular structure.
Fig. 3 is thermogravimetric weightlessness (TG-DSC) figure of Mg-Al-LDH and Mg-Al-CMC.As seen from the figure, Mg-Al-LDH discharges physical absorption water at about 110 DEG C, and the endothermic peak of about 230 DEG C is removing of the interlayer crystallization water, the decomposition combustion of organic matter species between the respective layer of about 370 DEG C.Corresponding said process, there are 3 obvious weightless platforms in TG curve.The TG figure of Mg-Al-CMC reflects 3 zero-g periods, and room temperature to 240 DEG C loses adsorption water and intermediary water; 257 ~ 380 DEG C is removing of the interlayer crystallization water; About 440 DEG C is the decomposition combustion of interlayer CMC, and corresponding TG curve weight loss is larger; The known Mg-Al-CMC of comprehensive FTIR and TG-DSC analysis result is not the simple composite of CMC and LDHs, but defines the inorganic-organic super molecular compound with intercalation configuration, and there is stronger interaction between main, object.
Fig. 4 is high-resolution field emission scanning electron microscope (HRSEM) figure of Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC in embodiment 1.As seen from the figure, Mg-Al-LDH has leaf load shape hierarchy, and the Mg-Al-LDO lamellar structure obtained after calcining disappears, and presents particle/block shape; And Mg-Al-CMC reverts to uniform laminated structure again.
The absorption property method of testing of material to boron is as follows:
Under room temperature, Mg-Al-LDH, Mg-Al-LDO and Mg-Al-CMC of taking 0.1g respectively join 100mL 30 μ gmL
-1sodium tetraborate simulated wastewater, being placed in mixing speed on magnetic stirring apparatus is 300 rmin
-1, in reaction different time points as 20,40,60min until 8h sampling, centrifugation, gets its absorbance of supernatant azomethine hydrogen spectrophotometry, and calculates adsorption capacity q(mgg
-1),
formula (1)
In formula:
c 0 for adsorbing the concentration of Inorganic Boron in front waste water, μ gmL
-1;
cfor the concentration of Inorganic Boron in waste water in adsorption process, μ gmL
-1;
vfor the cumulative volume (mL) of absorption system;
m 0 quality is added for adsorbent.
Fig. 5 be in embodiment 1 Mg-Al-LDH and Mg-Al-CMC to the adsorption effect figure of boron.As can be seen from the figure, the adsorption capacity of Mg-Al-CMC will apparently higher than Mg-Al-LDH, nearly 9 mgg of maximum adsorption capacity
-1.
Embodiment 2
(1) mol ratio is the synthesis of the Mg-Al houghite of 3: by 7.68g magnesium nitrate and 3.75g aluminum nitrate, be dissolved in
Mixed solution is made in 100mL distilled water; Then 5.6g NaOH is dissolved in 100mL distilled water and is made into mixed ammonium/alkali solutions.Two solution are instilled in the three-neck flask having filled 100mL distilled water under room temperature constantly stirs.After dropwising, use 1molL
-1naOH regulates pH to 9-10, at room temperature Keep agitation 2h.By gained mixture filtering and washing for several times, thermostatic drying chamber 80 DEG C of dry 4h put into by gained solid, obtain Mg-Al-LDH2.
(2) Mg-Al-LDH2 solid is positioned in Muffle furnace and calcines after 4 hours at 450 DEG C, obtain white solid Mg-Al-LDO2.
(3) this Mg-Al-LDO2 ultrasonic cleaner is scattered in 100mL distilled water obtains Mg-Al-LDO2 suspension.(4) take after 6.0g CMC dissolves in 100mL distilled water, be added drop-wise in Mg-Al-LDO2 suspension, machinery stirs
Mix 4 hours, keep solution alkaline pH9-10 in flask; Crystallization 12 hours in 100 DEG C of baking ovens in the hydrothermal reaction kettle its mixture being transferred to polytetrafluoroethylene (PTFE), filter, washing, to dry at 80 DEG C, grinding, obtains Mg-Al-CMC2 sample.
Fig. 6 be in embodiment 1 in Mg-Al-CMC and embodiment 2 Mg-Al-CMC2 to the adsorption effect comparison diagram of boron.
Can find out from the graph, two kinds of composites are suitable to the adsorption capacity of boron, and Mg-Al-CMC2 a little more than Mg-Al-CMC, illustrates that this kind of material can be used as the boron in boron specific adsorbent adsorbing separation waste water or seawater to the adsorption capacity of boron.
The present invention is not limited to above-mentioned embodiment, and every have identical or close technical scheme with the present invention, all falls within protection scope of the present invention.The technology that the present invention does not describe in detail, shape, structure part are known technology.
Claims (7)
1. a carboxymethyl cellulose ion insertion hydrotalcite-like composite material: it is characterized in that, the chemical general formula of this composite is [M
2+ 1-xm
3+ x(OH)
2]
x+(A
-)
xmH
2o, wherein M
2+for Zn
2+, Ca
2+or Mg
2+, M
3+for Fe
3+or Al
3+, M
2+and M
3+be positioned on hydrotalcite main body laminate; A
2-for interlayer carboxymethyl cellulose anion; X is M
3+/ (M
2++ M
3+) molar ratio, 0.1≤x≤0.33; M is the number of intermediary water molecule, m=3-6; The crystal structure of this kind of material is the crystal structure of hydrotalcite-like materials.
2. a preparation method for carboxymethyl cellulose ion insertion hydrotalcite-like composite material according to claim 1, its
Be characterised in that, comprise the following steps:
1) be dissolved in deionized water by soluble divalent metal salt and trivalent metal salt by certain mol proportion, stir to obtain solution A, wherein divalence and trivalent metal metal ion mol ratio are (1 ~ 4): 1, and bivalent metal ion concentration is 0.05 ~ 0.10 molL
-1;
2) under strong stirring, sodium hydroxide solution is dropwise added drop-wise in solution A, pH to 9 ~ 10 are regulated with sodium hydroxide solution, at room temperature Keep agitation 1 ~ 3h, by gained mixture filtering and washing for several times to neutral, thermostatic drying chamber 80 ~ 120 DEG C of drying 4 ~ 6h put into by gained filter cake, obtain white solid B, i.e. layered double hydroxide material LDH;
3), after calcining 3 ~ 5h at above-mentioned gained solid B being placed in Muffle furnace 300 ~ 600 DEG C, white solid powder C is obtained, i.e. layered bi-metal composite oxides LDO;
4) by above-mentioned obtained layered bi-metal composite oxides LDO, be scattered in by a certain percentage in deionized water, obtain LDO suspension D;
5) sodium carboxymethylcellulose solid is dissolved in distilled water, obtains carboxymethylcellulose sodium solution E;
6) by above-mentioned steps 4) in the LDO suspension D of gained, mix with a certain proportion of carboxymethylcellulose sodium solution E, mechanical agitation 6 ~ 10h, solution alkaline pH8 ~ 10 in maintenance flask; Crystallization 12 ~ 20h in 80 ~ 150 DEG C of baking ovens in hydrothermal crystallizing still said mixture being transferred to polytetrafluoroethylene (PTFE), be cooled to room temperature, products obtained therefrom Separation of Solid and Liquid, washing is to neutral rear 60 ~ 85 DEG C of vacuum drying 2 ~ 10h, obtain the hydrotalcite-like composite material of carboxymethyl cellulose intercalation, be designated as LDH-CMC.
3. preparation method according to claim 2, is characterized in that, described divalent metal divalent metal salt is Zn
2+, Ca
2+or Mg
2+nitrate, trivalent metal salt is Fe
3+or Al
3+nitrate.
4. preparation method according to claim 2, is characterized in that, described naoh concentration is 0.50 ~ 4.0 molL
-1, the mixing speed of described strong stirring is 300 ~ 450rpm.
5. preparation method according to claim 2, is characterized in that, the mol ratio of described sodium carboxymethylcellulose and trivalent salt is 1:1 ~ 3:1.
6. preparation method according to claim 2, it is characterized in that, described layered bi-metal composite oxides LDO and the mass ratio of deionized water are 1% ~ 3%, the concentration of described carboxymethylcellulose sodium solution E is 1% ~ 3%, and described LDO suspension D and the volume ratio of carboxymethylcellulose sodium solution E are 1:1 ~ 1:3.
7. the application in the adsorbing separation of a carboxymethyl cellulose ion insertion hydrotalcite-like composite material according to claim 1 boron in water body.
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